JPS63310715A - Novel crystalline silicate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel crystalline silicates and their preparation and the novel silicates thus produced.The present invention also relates to the use of the novel silicates as molecular sieves and as catalyst supports.

Synthetic crystalline materials are of general interest.

Crystalline aluminosilicates, often referred to as synthetic zeolites, have found wide industrial use, for example as catalysts, catalyst supports and as molecular sieves in catalytic and hydrogenolysis, and therefore much attention has been paid to their synthesis. It has been paid and is being paid again. Apart from the mostly classical zeolites, crystalline silicates have also been reported in the art. Examples of materials of this kind are ZSM-//, Z
Here new synthesized crystalline silicates, including silicates with structures designated as SM-/, 2O and ZSM-32, are obtained when specific molar ratios of the forming components are used and when specific aliphatic nitrogen-containing cations are used. It has been found that crystallinity can be produced from a solution.

Thus, the present invention, in its synthesized form, has the formula: %Formula %) where M represents an n-valent alkali metal or alkaline earth metal, TMA represents a tetramethylammonium cation, and 0≦p<0. 3;O0Q/〈qkuQ,!1t;0≦r〈
0.01 and 0≦Hatake≠).

The invention is particularly directed to synthetic crystalline silicates containing no or only limited amounts of alumina in their structure, ie 810□:Al2O5 molar ratio io.

Concerning silicates of 200 to 200 mm in size.

In particular, the present invention provides that in the above formula, and represents an alkali metal cation, and p(0,/j :0.Q, zz<q<
0.3j: r<0.01 and 0. /<1<2. Silicates with a rather low content of alkaline earth metal moieties in their structure, i.e. p0
．． Preference is given to silicates in which 1; 0.0'A<q 0.3: r<0.003 and 0.3 m</-76.

An example of a new synthetic crystalline silicate according to the present invention is a 5O8-/ Other examples include structures shown in synthesized form with the formula %):
Contains a structure designated as 5CS-2 with a line diffraction pattern.

Crystalline silica) SC8-2 can be suitably dried and baked to remove at least some of the water from the synthesized product along with at least some of the tetramethylammonium cation. This may be carried out at temperatures up to about ≠70° C. while maintaining a substantial portion of the crystallinity of the product. ■Yaki≠Q
Preferably, it is carried out at a temperature of 0 to 10°C.

Other examples have the formula % in synthesized form (where r (0,01 ) and the X
Contains a structure designated as 5C8-Hiroshi with a line diffraction pattern.

The present invention also provides a(M2/no):bTMA20:51o2:cA12
o3:dH2o (in the formula, M represents an n-valent alkali metal or alkaline earth metal, TMA represents a tetramethylammonium cation, and O≦a<0.:0.〈b〈10:0≦ c〈0.01 and j(a(
100, and the molar ratio of OH-78,102 is at least 0.3). Holding the elevated temperature for a sufficient period of time is followed by separation of the resulting crystalline material. The present invention relates to the synthesis method.

As used herein, the expression OH- includes hydroxide ions added to the forming solution derived from both tetramethylammonium hydroxide and a suitable metal hydroxide; the resulting product is an alumina-containing scale. It should be noted that

Albas can be introduced into the structure when using a forming solution containing (optionally) an alkali (earth) cation, a tetramethylammonium cation, a silica source, an alumina source and water within the above molar ranges.

A preferred method for producing crystalline silicates which optionally contain small amounts of alumina in their structure is based on the following molar relationship between the various constituents: 0≦&<0.2j: 0. /<b<2: O≦e×0.00j and ? (d(j has O and OH-75102 molar ratio is O6≠ or /
The general formula R1R2 includes using a mixture where J
O; SiO20 (wherein R1 and R2 are (substituted)
(representing a hydrocarbon group and one of R1 and R2 may represent a hydrogen atom) is used in the forming solution (provided that the molar ratio R1 is not higher than 10).
Crystalline silicate gold according to the invention can also be synthesized by applying R2O: 5102). Preferably, when using compounds according to the general formula R1R2O,
A R1R2O:5tO2 molar ratio lower than 2 is applied.

Examples of compounds according to the general formula R1R2O; SiO,O include alcohols such as methanol, ethanol and mixtures thereof, and ethers such as methoxymethane, ethoxyethane and mixtures thereof and low molecular weight cyclic ethers.

It should be noted that alkali and alkaline earth ions and nitrogen-containing cations may be added in the form of hydroxides and/or appropriate salts.

The process according to the invention is generally carried out at 73°C to 230°C, especially at 73°C to 230°C.
It is carried out at a temperature of 23°C to 2.23'C.

Typically, new crystalline structures are formed under suitable conditions in the forming solution at 72
This occurs when held for a time ranging from 7 to 7jO hours to allow formation of a reasonable amount of the appropriate structure.

Preferably, the process according to the invention is carried out for a period of time ranging from 21 I to 00 hours.

It has been found that stirring is sometimes advantageously applied in producing the desired synthetic crystalline silicate from the forming solution. Structures 5C8-1 and SCS-≠ may be suitably prepared when the forming mixture is held at about 0.degree. C.-0.degree. C. for a sufficient period of time under continuous stirring.

In order to increase the amount of suitable metals present or to be incorporated in the system, one can subject the crystalline silicates according to the invention to a metallization treatment. A preferred metallization treatment is the addition of aluminum and/or aluminum into the crystalline silicate according to the invention.
%, the incorporation of aluminum moieties is of interest to increase the number of acid sites in the system, including the incorporation of gallium moieties. Metallization may be carried out by methods known in the art.

The novel compounds according to the invention can optionally be used as molecular sieves (
(part) drying and/or (ii) annealing, and can be used as a catalyst support. In particular, alumina-containing crystalline silicate
They can be used as supports in the production of catalytically active species, for example by incorporating therein catalytically active metals.

Next, the present invention will be explained with reference to examples.

2j Titetramethylammonium hydroxide solution (F
lukm)j4+L grams and silica (Bak
1.3 from er! Dehydrated at Q °C > to Durum mixed together molar composition / Tetramethylamsonium hydroxide: / 8102: /! A mixture with H20 was obtained. This mixture is stirred/! It was held at θ°C for 72 hours.

After cooling, molar composition 0, /gTMA, O:SiO2:(AI,O,),:O
, n, O (where r<01)/) and an X-ray diffraction pattern shown in Table IK below was obtained.

Table l /30g±o, r vs Hiro, r±0.7 M3, t±0. / M3, lAD±0.0J: M2.70±0. (The yield of B M compound 5cs-i was Hiro≠% by weight (calculated based on the amount of 5tO2 present in the forming solution). The crystallinity of the product obtained was 1oos.

The above real numbers with similar starting materials but I2. ! 810 of
2: Repeat using a concentrated tetramethylammonium hydroxide solution to give a ratio of 20 moles of llI. The mixture under static conditions! Hold at θ℃ for 762 hours,
No detectable product was produced.

The mixture was kept at the same temperature under static conditions for an additional I4 time. 5C8-/ was produced along with some amorphous material.

The above experiment was carried out using tetramethylammonium hydroxide, 8
102 and I20 in a molar ratio of 0. ! Tetramethylammonium hydroxide: 8102: / 2. ,! ;
I20 was used and repeated. 0.0% tetramethylammonium chloride. was added to give a CI-/810□ ratio of j. The mixture was held under static conditions at 730°C for 76 hours to produce 5O8-/ along with amorphous material.

, 2J wt% tetramethylammonium hydroxide solution (from F'1uks+) 36≠ grams and silica (from Bak@r, dehydrated at 3!Q °C)
The mixture was mixed together to form a mixture having the following composition: /tetramethylammonium hydroxide: /SiO2: /jH20. This mixture under static conditions/! 76 at θ℃?
Holds time. After this time, a small amount of new silica) S
O8-2 could be isolated. This mixture was kept under the same conditions for an additional hour to produce 5CS along with the amorphous material. The molar composition of the synthesized crystalline compound was 0, (7J" TMA20:SiO2: (Al2O2)
r:Q, H20 (where r<0.01), and it has the X-ray diffraction pattern shown in Table H.

Table ■ ri, θ±θ, / M l, 3±0. /　　　M Otsu, Otsu ±0. /　　　M 6.3±0.1　M ≠、j10、／　　　　M ≠, 3±0. /　　　M Hiroshi, λ±0.1　M ≠, Q±o, i vs The amount of 5C8-1 obtained was 73% by weight.

Other forms of crystalline compound 5C8-2 could be prepared as follows: IA 7 grams of tetramethylammonium hydroxide (23% from Fluke), /! grams of silica (B
ak@rkamono and dehydrated at SiO ℃) and 22
A clear solution of gram of water is evaporated to give a solution with a composition of 0.2!
TMA20: 810. : A forming solution containing 12JI120 was obtained. ? - under static conditions Vci
s.

C for at least 76 hours, after which a crystalline silicate) SC8-2 could be isolated.The molar composition of the synthesized silicate was 0.07TMA20:SiO,:0. ．． It was 2 H2O. The 5O8-2 compound was obtained with 100% crystallinity.

A clear solution of 30 grams of tetramethylammonium hydroxide and water containing also O1≠ grams of sodium chloride was prepared to give the molar composition (7-0jNa20:/tetramethylammonium hydroxide:StO□:/
Forming solution with j H2O. This mixture/
No product was obtained when stirred at J-0°C for 72 hours. When the mixture was kept under the same conditions for an additional 2 hours, the new silica) SC8-≠ was 35 times crystalline with 700% crystallinity.
The molar composition of the 0 synthesized compound 5CS-≠ produced with a yield of 0.07N&,O:0. /TMA20: 8102:
0.4H20, and it has the X-ray diffraction pattern shown in Table 3.

Table ■ //, 3±0.2　M ! , 7±0. / VS ≠0.2±0. /　　　M 3, g±0. /　　　S 3.23+0.0J'M 3.IO±0. Oj　M λ, tS±0.0! M

Claims (1)

[Claims] (1) Formula when synthesized: (M_2_/_nO)_p:(TMA_2O)_q:S
iO_2:(Al_2O_3)_r:(H_2O)_s
(In the formula, M represents an n-valent alkali metal or alkaline earth metal, TMA represents a tetramethylammonium cation, and 0≦p<0.3;0.01<q<0.4;0≦r< 0.
01 and 0≦s<4). (2) M represents an alkali metal cation and p<0
．． 15; 0.025<q<0.35;r<0.01 and 0.1<s<2. (3) p<0.1;0.04<q<0.3;r<0.0
05 and 0.3<s<1.75. (4) Formula (0.10-0.20)TMA_2O:SiO_2:(
Al_2O_3)_r: (0.5-1.5)H_2O(
r<0.01) and at least the following lines: \D plane spacing (Å)\\Intensity\ 13.8±0.2 VS 4.8±0.1 M 3.8±0. Silicate SCS-1 with an X-ray diffraction pattern containing 1 M 3.40±0.05 M 2.70±0.05 M. (5) Formula (0-0.1) Na_2O: (0.025-0.20) when synthesized
TMA_2O:SiO_2:(Al_2O_3)_r:
(0.1-1.5)H_2O (where r<0.01) and at least the following line: ￥D Plane Spacing (Å)￥￥Intensity￥9.0±0.1 M 8.3 ±0.1 M 6.6±0.1 M 6.3±0.1 M 4.5±0.1 M 4.3±0.1 M 4.2±0.1 M 4.0±0 Silicate SCS-2 with an X-ray diffraction pattern containing .1 VS. (6) Formula (0-0.1)Na_2O:(0.05-0.25)T when synthesized
MA_2O:SiO_2:(Al_2O_3)_r:(
0.3-1.5) H_2O (where r<0.01) and at least the following lines: .1 VS 4.2±0.1 M 3.8±0.1 M 3.25±0.05 M 3.10±0.05 M 2.85±0.05 M silicate SCS-4. (7) Molar composition a (M_2_/_nO): bTMA_2O:SiO_2
:cAl_2O_3:dH_2O (where 0≦a<0.
5; 0.05<b<10;0≦c<0.01 and 5<
d<100 and the molar ratio OH-/SiO_2 is at least 0.3), comprising: The method of synthesis comprises holding the mixture at an elevated temperature for a period sufficient to form a crystalline material, and then separating the resulting crystalline material. (8) 0≦a<0.25;0.1<b<2;0≦c<0
．． 005 and 8<d<50 and OH-/Si
A mixture having a molar composition in which the O_2 molar ratio is between 0.4 and 1.5 is held at an elevated temperature for a period sufficient to form a crystalline material, and the resulting crystalline material is then separated. The method described in Section 7. (9) The forming solution has the formula R_1R_2O, where R_1 and R_2 represent (substituted) hydrocarbon groups and R_
1 and R_2 may represent a hydrogen atom), and the molar ratio R_
9. Process according to claim 7 or 8, in which 1R_2O; SiO_2 is not higher than 10. (10) The method of claim 9, using a forming solution having a R_1R_2O:SiO_2 ratio of at most 2. (11) A method according to any one of claims 7 to 10, wherein the temperature is maintained between 75°C and 250°C, in particular between 125°C and 225°C. (12) The forming solution is subjected to crystallization conditions from 12 to 750
12. A method according to any of claims 7 to 11, wherein the method is maintained for a period of time, in particular from 24 to 500 hours. (13) Crystalline silicate SCS-1 as defined in claims 4 and 6 by the method according to one or more of claims 7-10 while applying stirring to the formed mixture and a method of manufacturing SCS-4. (14) Use of the silicate according to one or more of claims 1 to 6, which may have been subjected to drying and/or baking treatment, as a molecular sieve. (15) Use of the silicate according to one or more of claims 1 to 6, which may have been subjected to drying and/or calcination treatment, as a catalyst support.